Plant-protecting substituted isoxazolines, isoxazoles, isothiazolines and isothiazoles, and also processes for their preparation and their use

ABSTRACT

Plant-protecting substituted isoxazolines, isoxazoles, isothiazolines and isothiazoles, and also processes for their preparation and their use 
     Compounds of the formula I 
     
         (R.sup.1)(R.sup.2)(R.sup.3)Si--A--Het--B--CO--Z            (I) 
    
     where 
     Het is an isoxazole-, isoxazoline-, isothiazole- or isothiazoline-3,5-diyl radical, 
     A and B are a bond or alkylene, 
     R 1 , R 2  and R 3  are substituted or unsubstituted, saturated or unsaturated alkyl or, if desired, phenylalkyl or phenyl, 
     Z is OH, OR where R is saturated or unsaturated, substituted or unsubstituted alkyl or substituted or unsubstituted phenyl or benzyl or trialkylsilylmethoxy, substituted or unsubstituted phenylamino or oxazolinyl or amino, mono- or dialkylamino or -hydrazino, cycloalkylamino, NH 2  NH 2 , pyridino, morpholino, dimethylmorpholino, a radical --ON═CR 4  R 5  or O--CHR 7  --CO--OR 6  where R 4 , R 5  =alkyl and/or R 4  CR 5  is cycloalkyl and R 6 , R 7  are H or a saturated or unsaturated acyclic hydrocarbon radical, 
     are suitable for protecting crop plants against phytotoxic side effects of herbicides.

DESCRIPTION

The invention relates to safeners or antidotes which, in combinationwith herbicides, can reduce the phytotoxicity of the herbicides to cropplants.

The invention relates to plant-protecting compounds of the generalformula (I) or salts thereof

    (R.sup.1)(R.sup.2)(R.sup.3)Si--A--Het--B--CO--Z            (I)

in which

Het is a divalent heterocyclic radical from the group comprising theisothiazolines, isothiazoles or isoxazoles, and isoxazolines of theformulae (Ia) to (Id), ##STR1## in which X is an oxygen or sulfur atom,

A and B independently of one another in each case are a single bond orC₁ -C₄ -alkylene which is unsubstituted or monosubstituted orpolysubstituted by C₁ -C₄ -alkyl,

R¹, R² and R³ independently of one another are alkyl, alkenyl, alkynylor cycloalkyl, it being possible for the four last-mentioned radicals tobe unsubstituted or mono- or polysubstituted by radicals from the groupcomprising alkoxy, alkylthio, mono- or dialkylamino, alkoxycarbonyl,alkylcarbonyloxy, cyano and halogen, furthermore phenylalkyl or phenylwhich in each case are unsubstituted or mono- or polysubstituted in thephenyl radical by radicals from the group comprising alkyl, alkoxy,alkylthio, mono- and dialkylamino, alkoxycarbonyl, cyano and halogen,

Z is hydroxyl or alkoxy, alkenyloxy, alkynyloxy, alkylthio, cycloalkoxy,phenoxy or benzyloxy, the 7 last-mentioned radicals being unsubstitutedor mono- or polysubstituted by radicals from the group comprisingalkoxy, alkylthio, mono- and dialkylamino, phenyl, substituted phenyl,cyano, haloalkyl, haloalkoxy and halogen,

furthermore trialkylsilylmethoxy, a radical of the formula (Ie) or (If)##STR2## where R is hydrogen or alkyl, Z¹ radicals independently of oneanother are halogen, halogenoalkyl, halogenoalkoxy, alkyl, alkoxy oralkylthio and n is an integer from 0 to 5, or

Z is furthermore amino, mono- or dialkylamino, cycloalkylamino,hydrazino, alkyl- or dialkylhydrazino, pyridino, morpholino,dimethylmorpholino, a radical of the formula (Ig), ##STR3## where R⁴ andR⁵ independently of one another are alkyl radicals or R⁴ and R⁵ togetherwith the carbon atom linking them form a cycloalkyl radical, furthermorea radical of the formula (Ih), ##STR4## where R⁶ and R⁷ independently ofone another are hydrogen or a saturated or unsaturated acyclichydrocarbon radical.

In formula (I), alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino andalkylthio radicals in the alkyl moiety as well as the correspondingunsaturated and/or substituted radicals in the hydrocarbon moiety can ineach case be straight-chain or branched. Alkyl radicals, also in thecompound meanings such as alkoxy, haloalkyl etc., are, for example,methyl, ethyl, n- and i-propyl, n-, i-, t- and 2-butyl, the isomericpentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecylradicals, and also the longer-chain fatty alkyl radicals having up to 24carbon atoms. Alkenyl and alkynyl radicals mean the unsaturated radicalswhich are possible and which correspond to the alkyl radicals,preferably (C₂ -C₁₂)-alkenyl and -alkynyl radicals. Halogen is fluorine,chlorine, bromine or iodine, preferably fluorine, chlorine or bromine,in particular fluorine or chlorine.

In the case where Z═OH, the compounds of the formula (I) can form salts.Salts which can be employed according to the invention are those whichcan be used in agriculture. Examples of suitable salts are metal saltssuch as alkali metal salts or alkaline earth metal salts, in particularsodium salts or potassium salts, ammonium salts or substituted ammoniumsalts which are mono- to tetrasubstituted by alkyl and/or alkanolradicals having preferably up to 4 carbon atoms.

Formula (I) furthermore also embraces all stereoisomers and theirmixtures, in particular also pure enantiomers and their mixtures (forexample racemates). Stereoisomers can occur mainly when asymmetriccarbon atoms or suitably substituted double bonds are present in theformula (I). An example of an asymmetric carbon atom is the carbon atombonded to the oxygen atom in the isoxazoline ring.

Plant-protecting compounds of the formula (I) according to theinvention, or salts thereof, which are of particular interest are thosein which

Z is hydroxyl, C₁ -C₆ -alkoxy, C₂ -C₆ -alkynyloxy, C₂ -C₆ -alkynyloxy,C₁ -C₆ -alkylthio, C₃ -C₆ -cycloalkoxy, phenoxy or benzyloxy, the 7last-mentioned radicals being unsubstituted or mono- or polysubstitutedby radicals from the group comprising C₁ -C₄ -alkoxy, mono- or di-(C₁-C₄ -alkyl)amino, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkyl, C₁ -C₄-haloalkoxy, cyano and halogen, or

Z is furthermore tri(C₁ -C₄ -alkyl)silylmethoxy, furthermore a radicalof the formula (Ie) or (If) mentioned, in which R in each case ishydrogen or (C₁ -C₄)-alkyl, Z¹ is halogen and n is 0, 1, 2, 3, 4 or 5,or

Z is furthermore amino, mono- or di-(C₁ -C₄ -alkyl)amino, C₅ -C₆-cycloalkylamino, hydrazino, piperidino, morpholino or2,6-dimethylmorpholino, a radical of the formula (Ig) mentioned where R⁴and R⁵ independently of one another are C₁ -C₄ -alkyl or R¹ and R²together with the carbon atom linking them form a 5-, 6- or 7-memberedcycloalkyl radical, or

Z is a radical of the formula (Ih) mentioned where R⁶ and R⁷independently of one another are hydrogen or C₁ -C₆ -alkyl, C₂ -C₆-alkyl or C₂ -C₆ -alkynyl.

Compounds of the formula (I) according to the invention, or saltsthereof, which are of particular interest are those where R¹, R² and R³independently of one another are C₁ -C₁₈ -alkyl, C₂ -C₁₈ -alkenyl, C₂-C₁₈ -alkynyl or C₃ -C₁₈ -cycloalkyl, the 4 last-mentioned radicalsbeing unsubstituted or mono- or polysubstituted by radicals from thegroup comprising C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio, mono- or di-(C₁ -C₄-alkyl)amino, (C₁ -C₄ -alkoxy)carbonyl, (C₁ -C₄ -alkyl)carbonyloxy,cyano and halogen, furthermore phenyl-(C₁ -C₄ -alkyl) or phenyl, the 2last-mentioned radicals being unsubstituted or mono- or polysubstitutedby radicals from the group comprising C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁-C₄ -alkylthio, mono- and di-(C₁ -C₄ -alkyl)amino, cyano and halogen.

Preferred compounds of the formula (I) according to the invention, orsalts thereof, are those where

Z is hydroxyl, C₁ -C₄ -alkoxy, C₂ -C₄ -alkenyloxy, C₂ -C₄ -alkynyloxy,C₁ -C₄ -alkylthio, phenoxy or benzyloxy, the 6 last-mentioned radicalsbeing unsubstituted or mono- or polysubstituted by radicals from thegroup comprising C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, mono-or di-(C₁ -C₄ -alkyl)amino, cyano and halogen, furthermore tri-(C₁ -C₂-alkyl)silylmethoxy, a radical of the formula (Ie) or (If) mentionedwhere R is hydrogen or C₁ -C₄ -alkyl, Z¹ is halogen and n is 0-5,

furthermore mono- and di-(C₁ -C₄ -alkyl)amino, C₅ -C₆ -cycloalkylamino,a radical of the formula (Ih) mentioned where R⁶ is C₁ -C₄ -alkyl, C₂-C₄ -alkenyl or C₂ -C₆ -alkynyl and R⁷ is hydrogen or methyl.

Other preferred compounds of the formula (I) according to the invention,and salts thereof, are those where

A is a direct bond or C₁ -C₂ -alkylene, preferably a direct bond or CH₂,and

B is a direct bond or C₁ -C₂ -alkylene, preferably a direct bond or CH₂.

Equally, preferred compounds of the formula (I) according to theinvention, or salts thereof, are those where R¹, R² and R³ independentlyof one another are C₁ -C₆ -alkyl, in particular methyl, ethyl, n- ori-propyl, n-, i-, t- or 2-butyl, pentyl, n-, i- and 2-hexyl, phenyl orbenzyl. Particularly preferred compounds of the formula (I) according tothe invention are those in which A, B, Z, Z¹, n, R, R¹, R², R³ and X ineach case have meanings which have been mentioned as being preferred.

The present invention also relates to a process for the preparation ofthe compounds of the formula (I) and salts thereof, which comprisesreacting a compound of the formula (II) or (III)

    (R.sup.1)(R.sup.2)(R.sup.3)Si--A--CH═CH.sub.2          (II)

    (R.sup.1)(R.sup.2)(R.sup.3)Si--A--CH═CH.sub.2          (III)

where R¹, R², R³ and A have the meanings given in the case of formula(I), with a nitrile oxide of the formula (IV), ##STR5## where Z and Bhave the meanings given in the case of formula (I), or reacting acompound of the formula (V) or (VI),

    H.sub.2 C═CH--B--CO--Z                                 (V)

    HC.tbd.C--B--CO--Z                                         (VI)

where B and Z have the meanings given in the case of formula (I), with acompound of the formula (VII)

    (R.sup.1) (R.sup.2) (R.sup.3)Si--A--C.sup.(+) ═N--O.sup.(-)(VII)

where R¹, R², R³ and A have the meanings mentioned above in the case offormula (I).

Suitable solvents for the reactions are nonpolar organic solvents, forexample ethers such as diethyl ether or THF. However, the reactions canalso be carried out in the absence of solvents.

The starting compounds of the formulae (II) and (VII) are known from theliterature (cf. J. Org. Chem. 25, 1160 (1960); J. Med. Chem. 17 (1974),549-552; J. Chem. Soc. Chem. Commun. 1984, 968-969; Can. J. Chem. 41,2980 (1963), J. Am. Chem. Soc. 95, 6152 (1973), Fieser and Fieser inReagents for Organic Synthesis 10, 6 and 11, 16; and the particularreferences mentioned therein) or can be prepared analogously to thecompounds which are known.

The compounds of the formula (I) reduce or inhibit phytotoxic sideeffects which can occur when herbicides are employed in crops of usefulplants.

The compounds of the formula (I) and the herbicidal active substancescan be applied together or one after the other, in any sequence desired.The compounds of the formula (I) are then capable of reducing, orcompletely compensating for, harmful side effects of the herbicides incrop plants, without impairing the activity of these herbicides againstharmful plants.

As a result of this, the field of application of conventional plantprotection agents can be widened very considerably. Such compounds whichpossess the property of protecting crop plants against phytotoxic damageby herbicides are called "antidotes" or "safeners".

Examples of herbicides whose phytotoxic side effects can be reduced bymeans of the compounds of the formula (I) are carbamates,thiocarbamates, haloacetanilides, substituted phenoxy-, naphthoxy-,phenoxyphenoxy-, benzyloxyphenoxy- and heteroaryloxyphenoxy-carboxylicacid derivatives as well as cyclohexanedione derivatives. Examples ofheteroaryloxyphenoxy-carboxylic acid derivatives are quinolyloxy-,quinoxalyloxy-, pyridyloxy-, benzoxazolyloxy- andbenzothiazolyloxy-phenoxycarboxylic acid esters. Preferred compounds arephenoxyphenoxy- and heteroaryloxyphenoxy-carboxylic acid esters.Suitable esters in this connection are, in particular, lower alkyl,alkenyl and alkynyl esters.

The following herbicides may be mentioned by way of example but withoutimposing any restriction:

A) Herbicides of the type of the (C₁ -C₄) alkyl, (C₂ -C₄)-alkenyl or (C₃-C₄)alkynyl phenoxyphenoxy-, benzylphenoxy andheteroaryloxyphenoxy-carboxylates, such as methyl2-(4-(2,4-dichlorophenoxy)phenoxy)propionate, methyl2-(4-(4-bromo-2-chlorophenoxy)phenoxy)propionate, methyl2-(4-(4-trifluoromethylphenoxy)phenoxy)propionate, methyl2-(4-(2-chloro-4-trifluoromethylphenoxy)phenoxy)propionate, methyl2-(4-(2,4-dichlorobenzyl)phenoxy)propionate, ethyl4-(4-(4-trifluoromethylphenoxy)phenoxy)pent-2-enoate, ethyl2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)propionate, propargyl2-(4-(3,5-dichloropyridyl-2-oxy) phenoxy)propionate, ethyl2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy)propionate, methyl2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate, butyl2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate, methyl2-(4-(3-fluoro-5-chloropyridyl-2-oxy) phenoxy)propionate, propargyl2-(4-(3-fluoro-5-chloropyridyl-2-oxy)phenoxy)propionate, methyl2-(4-(6-chloro-2-quinoxalyloxy)phenoxy)propionate, methyl2-(4-(6-fluoro-2-quinoxalyloxy)phenoxy)propionate, methyl2-(4-(6-chloro-2-quinolyloxy)phenoxy)propionate, 5-methoxycarbonylmethyl2-(4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy)thiopropionate,

B) Chloroacetanilide herbicides, such asN-methoxymethyl-2,6-diethylchloroacetanilide,N-(3'-methoxyprop-2'-yl)methyl-6-ethylchloroacetanilide,N-(3-methyl-1,2,4-oxadiazol-5-ylmethyl)-2,6-dimethylchloroacetanilide,

C) Thiocarbamates, such as S-ethyl N,N-dipropylthiocarbamate or S-ethylN,N-diisobutylthiocarbamate,

D) Cyclohexanedione derivatives, such as methyl3-(1-allyloxyimino)butyl-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate2-(N-ethoxybutyrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one,2-(N-ethoxybutyrimidoyl)-5-(2-phenylthiopropyl)-3-hydroxy-2-cyclohexen-1-one,2-(1-allyloxyiminobutyl)-4-methoxycarbonyl-5,5-dimethyl-3-oxocyclohexenol,2-(1-(3-chloroallyloxy)iminobutyl)-5-(2-ethylthio)propyl)-3-hydroxycyclohex-2-enone2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-enone or2-(1-ethoxyiminopropyl)-5-(2,4,6-trimethylphenyl)-3-hydroxy-2-cyclohexen-1-one.

The ratio of safener:herbicide can vary within wide limits, preferablyin the range between 1:10 and 10:1, in particular between 2:1 and 1:10.The amounts of herbicide and safenet which are ideal in each case dependon the type of the herbicide used or on the safener used as well as onthe nature of the plant stand to be treated, and they can be determinedfor each individual case by appropriate experiments.

The safeners are mainly employed in particular in cereal crops (wheat,rye, barley, oats), rice, maize and sorghum, but also in cotton, sugarbeet, sugar cane and soya bean.

Depending on their properties, the safeners of the formula (I) can beused for pre-treating the seed of the crop plant (seed dressing), orthey can be incorporated in the seed furrows prior to sowing, or usedtogether with the herbicide prior to, or after, plant emergence.

Pre-emergence treatment includes both the treatment of the area undercultivation prior to sowing and treatment of the areas under cultivationwhere seed has been sown but growth of the crop plants has not yet takenplace. The application together with the herbicide is preferred. Tankmixes or ready mixes can be employed for this purpose.

The required application rates of the compounds of the formula (I) canvary within wide limits, depending on the indication and the herbicideused, and they generally vary between 0.01 and 10 kg of active substanceper hectare.

The present invention thus also relates to a method of protecting cropplants from phytotoxic side effects of herbicides, which comprisesapplying an effective amount of a compound of the formula (I) before,after or simultaneously with the herbicide to the plants, seeds ofplants, or the area under cultivation.

Moreover, the compounds according to the invention exhibitgrowth-regulatory properties in crop plants. They engage in the plantmetabolism in a regulating fashion and can therefore be employed forfacilitating harvests such as, for example, by triggering desiccation,abscission and stunted growth. Furthermore, they are also suitable forgenerally controlling and inhibiting undesirable vegetative growth,without killing the plants in the process. Inhibition of vegetativegrowth is very important in many monocotyledon and dicotyledon culturessince lodging can be reduced, or completely inhibited, by this process.

The compounds of the formula I or their combinations with one or more ofthe herbicides or groups of herbicides mentioned can be formulated in avariety of ways, as predetermined by the biological and/orchemiophysical parameters. The following possibilities are thereforesuitable for formulation: wettable powders (WP), emulsifiableconcentrates (EC), water-soluble powders (SP), water-solubleconcentrates (SL), concentrated emulsions (EW) such as oil-in-water andwater-in-oil emulsions, sprayable solutions or emulsions, capsulesuspensions (CS), dispersions on an oil or water basis (SC),suspoemulsions, suspension concentrates (SC), dusting agents (DP),solutions which are miscible with oil (OL), seed-dressing agents,granules (GR) in the form of microgranules, spray granules, coatedgranules and adsorption granules, soil granules or granules forbroadcasting (FG), water-soluble granules (SG), water-dispersiblegranules (WG), ULV formulations, microcapsules and waxes.

These individual formulation types are known in principle and aredescribed, for example, in: Winnacker-Kuchler, "Chemische Technologie[Chemical Technology]", Volume 7, C. Hauser Verlag Munich, 4th Ed.,1986; van Valkenburg, "Pesticides Formulations", Marcel Dekker N.Y., 2ndEd. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G.Goodwin Ltd. London.

The formulation auxiliaries required, such as inert materials,surfactants, solvents and other additives, are also known and aredescribed, for example, in: Watkins, "Handbook of Insecticide DustDiluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H. v.Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley &Sons, N.Y.; Marschen, "Solvents Guide", 2nd Ed., Interscience, N.Y.1950; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp.Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface ActiveAgents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt,"Grenzflachenaktive Athylenoxidaddukte" [Surface-active Ethylene OxideAdducts]", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler,"Chemische Technologie [Chemical Technology]", Volume 7, C. HauserVerlag Munich, 4th Ed. 1986.

Combinations with other pesticidally active substances, fertilizersand/or growth regulators may also be prepared on the basis of theseformulations, for example in the form of a readymix or as a tank mix.

The invention therefore relates to the agents which contain thecompounds of the formula (I) according to the invention. These aremainly, on the one hand, plant-protecting agents which contain one ormore compounds of the formula (I) and customary inert auxiliaries whichcorrespond to the particular type of formulation, and, on the otherhand, herbicidal agents which contain a combination of compounds of theformula (I) and one or more herbicides and the customary auxiliarieswhich correspond to the particular type of formulation.

Wettable powders are preparations which are uniformly dispersible inwater and which, besides the active substance, also contain wettingagents, for example polyoxyethylated alkylphenols, polyoxyethylatedfatty alcohols and fatty a mines, alkanesulfonates oralkylarylsulfonates, and dispersing agents, for example sodiumligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodiumdibutylnaphthalenesulfonate, or alternatively sodiumoleylmethyltaurinate, in addition to a diluent or inert substance.Emulsifiable concentrates are prepared by dissolving the activesubstance in an organic solvent, for example butanol, cyclohexanone,dimethylformamide, xylene and also higherboiling aromatic compounds orhydrocarbons, with the addition of one or more emulsifiers. Examples ofemulsifiers which can be used are: calcium salts of an alkylarylsulfonicacid, such as Ca dodecylbenzenesulfonate, or non-ionic emulsifiers, suchas fatty acid polyglycol esters, alkylaryl polyglycol ethers, fattyalcohol polyglycol ethers, propylene oxide/ethylene oxide condensationproducts (for example block copolymers), alkyl polyethers, sorbitanfatty acid esters, polyoxyethylene sorbitan fatty acid esters orpolyoxyethylene sorbitol esters.

Dusting agents can be obtained by grinding the active substance withfinely divided solid substances, for example talc or natural clays, suchas kaolin, bentonite, pyrophillite or diatomaceous earth.

Soil granules or granules for broadcasting can be produced either byspraying the active substance onto adsorptive, granulated inert materialor by applying active substance concentrates onto the surface ofcarriers, such as sand, kaolinites or granulated inert material, bymeans of binders, for example polyvinyl alcohol, sodium polyacrylate or,alternatively, mineral oils. Suitable active substances can also begranulated in the manner which is conventional for the production offertilizer granules, if desired in a mixture with fertilizers.

As a rule, the agrochemical preparations contain 0.1 to 99 percent byweight, in particular 0.1 to 95% by weight, of active substance of theformula (I), or of active substance mixture antidote/herbicide, 1 to 99%by weight, in particular 5 to 99.8% by weight, of a solid or liquidadditive and 0 to 25% by weight, in particular 0.1 to 25% by weight, ofa surfactant.

The concentration of active substance in wettable powders is, forexample, about 10 to 90% by weight, the remainder to 100% by weight iscomposed of conventional formulation components. In the case ofemulsifiable concentrates, the concentration of active substance can beabout 1 to 80% by weight. Formulations in the form of dusts usuallycontain 1 to 20% by weight of active substance, sprayable solutionsabout 0.2 to 20% by weight of active substance. In the case ofwater-dispersible granules, the active substance content depends partlyon whether the active compound is liquid or solid. As a rule, thewater-dispersible granules contain between 10 and 90% by weight.

In addition, the active substance formulations mentioned contain, ifappropriate, the adhesives, wetting agents, dispersing agents,emulsifiers, penetrants, solvents, fillers or carriers which areconventional in each case.

For use, the formulations, present in commercially available form, arediluted, if appropriate, in a customary manner, for example using waterin the case of wettable powders, emulsifiable concentrates, dispersionsand water-dispersible granules. Preparations in the form of dusts, soilgranules or granules for broadcasting and also sprayable solutions areusually not further diluted with other inert substances before use.

The application rate required for the compounds of the formula (I)varies with the external conditions, such as, inter alia, temperature,humidity, and the nature of the herbicide used. It can vary within widelimits, for example between 0.005 and 10.0 kg/ha or more of activesubstance, but is preferably between 0.01 and 5 kg/ha.

The examples which follow serve to illustrate the invention in greaterdetail:

A. Formulation Examples

a) A dust is obtained by mixing 10 parts by weight of a compound of theformula (I) or, if appropriate, a mixture of active substance with aherbicide and 90 parts by weight of talc as the inert substance andcomminuting the mixture in a hammer mill.

b) A wettable powder which is readily dispersible in water is obtainedby mixing 25 parts by weight of a compound of the formula (I) or anactive substance mixture of safener of the formula (I) with a herbicide,64 parts by weight of kaolin-containing quartz as the inert substance,10 parts by weight of potassium ligninsulfonate and 1 part by weight ofsodium oleoylmethyltauride as the wetting and dispersing agent, andgrinding the mixture in a pinned-disk mill.

c) A dispersion concentrate which is readily dispersible in water isobtained by mixing 20 parts by weight of a compound of the formula (I),if appropriate as a mixture with a herbicide with 6 parts by weight ofalkylphenol polyglycol ether (®Triton X 207), 3 parts by weight ofisotridecanol polyglycol ether (8 EO) and 71 parts by weight ofparaffinic mineral oil (boiling range, for example, about 255° to above277° C.), and grinding the mixture in a ball mill to a fineness of below5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of acompound of the formula (I) or an active substance mixture of safenet(I) and herbicide, 75 parts by weight of cyclohexanone as the solventand 10 parts by weight of oxyethylated nonylphenol as the emulsifier.

e) Water-dispersible granules are obtained by mixing

    ______________________________________                                        75 parts by weight                                                                          of a compound of the formula I,                                               if appropriate as a mixture with                                              a herbicide,                                                    10 parts by weight                                                                          of calcium ligninsulfonate,                                      5 parts by weight                                                                          of sodium lauryl sulfate,                                        3 parts by weight                                                                          of polyvinyl alcohol and                                         7 parts by weight                                                                          of kaolin,                                                      ______________________________________                                    

grinding the mixture in a pinned-disk mill, and granulating the powderin a fluidized bed while spraying on water as the granulation liquid.

f) Alternatively, water-dispersible granules are obtained byhomogenizing and comminuting

    ______________________________________                                        25 parts by weight                                                                          of a compound of the formula (I)                                              or a mixture of the compound with                                             a herbicide,                                                     5 parts by weight                                                                          of sodium 2.2'-dinaphthylmethane-                                             6,6'-disulfonate,                                                2 parts by weight                                                                          of sodium oleoylmethyltaurinate,                                1 part by weight                                                                            of polyvinyl alcohol,                                           17 parts by weight                                                                          of calcium carbonate and                                        50 parts by weight                                                                          of water                                                        ______________________________________                                    

in a colloid mill, subsequently grinding the mixture in a bead mill, andatomizing and drying the resulting suspension in a spray tower by meansof a single-fluid jet.

B. Chemical Examples

Methyl 5-trimethylsilyl-2-isoxazoline-3-carboxylate (Table 1, ExampleNo. 2)

3 g of vinyltrimethylsilane and 4.13 g of chloroximinomethyl acetate areintroduced into 150 ml of ether, and 4.1 g of triethylamine in 150 ml ofether are then slowly added dropwise. Water is subsequently added, andthe mixture is extracted several times using ether. The ether phase isdried using magnesium sulfate, concentrated on a Rotavapor and separatedover a silica gel column (solvent n-heptane:ethyl acetate 9:1)

Yield: 5.1 g of the desired pure substance.

    Refractive index n.sub.D.sup.20 =1.467

Ethyl 5-trimethylsilylmethyl-2-isoxazoline-3-carboxylate (Table 1,Example 3)

3.43 g of allyltrimethylsilane and 4.55 g of chloroximinoethyl acetateare introduced into 150 ml of ether. 3.03 g of triethylamine in 150 mlof ether are then slowly added dropwise. Water is subsequently added,and the mixture is extracted several times using ether. The ether phaseis dried over MgSO₄, and the ether is subsequently stripped off on aRotavapor. Separation over a silica gel column (solvent: n-heptane:etheracetate=8:2) gives 4.2 g of the desired pure substance of a refractiveindex n_(D) ²⁰ -1.462

The Examples listed in Tables 1-6 are obtained in an analogous manner.

The analogous carboxylic acids can also be prepared from thecorresponding esters, or, if desired, the esters can be prepared fromthe corresponding carboxylic acids, by methods known in principle.

    __________________________________________________________________________     ##STR6##                                            (1)                      __________________________________________________________________________    Example                                                                            R.sup.1                                                                              R.sup.2                                                                              R.sup.3     A    Z             Fp/n.sub.D.sup.20           __________________________________________________________________________     1   CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3    CH.sub.2                                                                           OH            103° C.               2   "      "      "           "    OCH.sub.3     1,467                        3   "      "      "           "    OC.sub.2 H.sub.5                                                                            1,462                        4   "      "      "           "    OC.sub.3 H.sub.7                           5   "      "      "           "    OCH(CH.sub.3).sub.2                        6   "      "      "           "    OC.sub.4 H.sub.9                                                                            1,462                        7   "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5         8   "      "      "           "    OC.sub.6 H.sub.5                           9   "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                  10  "      "      "           "    OCH.sub.2 CHCH.sub.2                                                                        1,4712                       11  "      "      "           "    OCH.sub.2 CCH 1,482                        12  "      "      "           "    O.sup.- Na.sup.+                           13  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3               14  "      "      "           "    N(CH.sub.3).sub.2                          15  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5      16  "      "      "           "    NH.sub.2                                   17  "      "      "           "    O.sup.- NH.sub.4.sup.+                     18  "      "      "           "    OCH.sub.3 CO.sub.2 CH.sub.3                19  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3             20  "      "      "           "    O.sup. - K.sup.+                           21  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2              __________________________________________________________________________    Example                                                                            R.sup.1                                                                              R.sup.2                                                                              R.sup.3     A    Z             n.sub.D.sup.20              __________________________________________________________________________     22  CH.sub.3                                                                             CH.sub.3                                                                             C.sub.6 H.sub.5                                                                           CH.sub.2                                                                           OH            1,530                        23  "      "      "           "    OCH.sub.3     1,5252                       24  "      "      "           "    OC.sub.2 H.sub.5                                                                            1,514                        25  "      "      "           "    OC.sub.3 H.sub.7                           26  "      "      "           "    OCH(CH.sub.3).sub.2                        27  "      "      "           "    OC.sub.4 H.sub.9                           28  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5         29  "      "      "           "    OC.sub.6 H.sub.5                           30  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                  31  "      "      "           "    OCH.sub.2 CHCH.sub.2                       32  "      "      "           "    OCH.sub.2 CCH                              33  "      "      "           "    O.sup.- Na.sup.+                           34  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3               35  "      "      "           "    N(CH.sub.3).sub.2                          36  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5      37  "      "      "           "    NH.sub.2                                   38  "      "      "           "    O.sup.- NH.sub.4.sup.+                     39  "      "      "           "    OCH.sub.3 CO.sub.2 CH.sub.3                40  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3             41  "      "      "           "    O.sup.- K.sup.+                            42  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2               43  CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                           CH.sub. 2                                                                          OH                                         44  "      "      "           "    OCH.sub.3                                  45  "      "      "           "    OC.sub.2 H.sub.5                           46  "      "      "           "    OC.sub.3 H.sub.7                           47  "      "      "           "    OCH(CH.sub.3).sub.2                        48  "      "      "           "    OC.sub.4 H.sub.9                           49  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5         50  "      "      "           "    OC.sub.6 H.sub.5                           51  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                  52  "      "      "           "    OCH.sub.2 CHCH.sub.2                       53  "      "      "           "    OCH.sub.2 CCH                              54  "      "      "           "    O.sup.- Na.sup.+                           55  "      "      "           "    OCH.sub.2 Si(CH.sub. 3).sub.3              56  "      "      "           "    N(CH.sub.3).sub.2                          57  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5      58  "      "      "           "    NH.sub.2                                   59  "      "      "           "    O.sup.- NH.sub.4.sup.+                     60  "      "      "           "    OCH.sub.3 CO.sub.2 CH.sub.3                61  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3             62  "      "      "           "    O.sup.- K.sup.+                            63  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2               64  CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                           CH.sub.2                                                                           OH                                         65  "      "      "           "    OCH.sub.3                                  66  "      "      "           "    OC.sub.2 H.sub.5                           67  "      "      "           "    OC.sub.3 H.sub.7                           68  "      "      "           "    OCH(CH.sub.3).sub.2                        69  "      "      "           "    OC.sub.4 H.sub.9                           70  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5         71  "      "      "           "    OC.sub.6 H.sub.5                           72  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                  73  "      "      "           "    OCH.sub.2 CHCH.sub.2                       74  "      "      "           "    OCH.sub.2 CCH                              75  "      "      "           "    O.sup.- Na.sup.+                           76  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3               77  "      "      "           "    N(CH.sub.3).sub.2                          78  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5      79  "      "      "           "    NH.sub.2                                   80  "      "      "           "    O.sup.- NH.sub.4.sup.+                     81  "      "      "           "    OCH.sub.3 CO.sub.2 CH.sub.3                82  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3             83  "      "      "           "    O.sup.- K.sup.+                            84  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2               85  CH(CH.sub.3).sub.2                                                                   CH(CH.sub.3).sub.2                                                                   CH(CH.sub.3).sub.2                                                                        CH.sub.2                                                                           OH                                         86  "      "      "           "    OCH.sub.3                                  87  "      "      "           "    OC.sub.2 H.sub.5                           88  "      "      "           "    OC.sub.3 H.sub.7                           89  "      "      "           "    OCH(CH.sub.3).sub.2                        90  "      "      "           "    OC.sub.4 H.sub.9                           91  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub. 5        92  "      "      "           "    OC.sub.6 H.sub.5                           93  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                  94  "      "      "           "    OCH.sub.2 CHCH.sub.2                       95  "      "      "           "    OCH.sub.2 CCH                              96  "      "      "           "    O.sup.- Na.sup.+                           97  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3               98  "      "      "           "    N(CH.sub.3).sub.2                          99  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5     100  "      "      "           "    NH.sub.2                                  101  "      "      "           "    O.sup.- NH.sub.4.sup.+                    102  "      "      "           "    OCH.sub.2 Cl.sub.2 CH.sub.3               103  "      "      "           "    OCH(CH.sub. 3)CO.sub.2 CH.sub.3           104  "      "      "           "    O.sup.- K.sup.+                           105  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2              106  C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                           CH.sub.2                                                                           OH                                        107  "      "      "           "    OCH.sub.3                                 108  "      "      "           "    OC.sub.2 H.sub.5                          109  "      "      "           "    OC.sub.3 H.sub.7                          110  "      "      "           "    OCH(CH.sub.3).sub.2                       111  "      "      "           "    OC.sub.4 H.sub.9                          112  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5        113  "      "      "           "    OC.sub.6 H.sub.5                          114  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                 115  "      "      "           "    OCH.sub.2 CHCH.sub.2                      116  "      "      "           "    OCH.sub.2 C CH                            117  "      "      "           "    O.sup.- Na.sup.+                          118  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3              119  "      "      "           "    N(CH.sub.3).sub.2                         120  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5     121  "      "      "           "    NH.sub.2                                  122  "      "      "           "    O.sup.- NH.sub.4.sup.+                    123  "      "      "           "    OCH.sub.3 CO.sub.2 CH.sub.3               124  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3            125  "      "      "           "    O.sup.- K.sup.+                           126  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2              127  CH.sub.3                                                                             CH.sub.3                                                                             (t)C.sub.4 H.sub.9                                                                        CH.sub.2                                                                           OH                                        128  "      "      "           "    OCH.sub.3                                 129  "      "      "           "    OC.sub.2 H.sub.5                          130  "      "      "           "    OC.sub.3 H.sub.7                          131  "      "      "           "    OCH(CH.sub.3).sub.2                       132  "      "      "           "    OC.sub.4 H.sub.9                          133  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5        134  "      "      "           "    OC.sub.6 H.sub.5                          135  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                 136  "      "      "           "    OCH.sub.2 CHCH.sub.2                      137  "      "      "           "    OCH.sub.2 CCH                             138  "      "      "           "    O.sup.- Na.sup.+                          139  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3              140  "      "      "           "    N(CH.sub.3).sub.2                         141  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5     142  "      "      "           "    NH.sub.2                                  143  "      "      "           "    O.sup.- NH.sub.4.sup.+                    144  "      "      "           "    OCH.sub.3 CO.sub.2 CH.sub.3               145  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3            146  "      "      "           "    O.sup.- K.sup.+                           147  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2              148  (n)C.sub.6 H.sub.13                                                                  (n)C.sub.6 H.sub.13                                                                  (n)C.sub.6 H.sub.13                                                                       CH.sub.2                                                                           OH                                        149  "      "      "           "    OCH.sub.3                                 150  "      "      "           "    OC.sub.2 H.sub.5                          151  "      "      "           "    OC.sub.3 H.sub.7                          152  "      "      "           "    OCH(CH.sub.3).sub.2                       153  "      "      "           "    OC.sub.4 H.sub.9                          154  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5        155  "      "      "           "    OC.sub.6 H.sub.5                          156  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                 157  "      "      "           "    OCH.sub.2 CHCH.sub.2                      158  "      "      "           "    OCH.sub.2 CCH                             159  "      "      "           "    O.sup.- Na.sup.+                          160  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3              161  "      "      "           "    N(CH.sub.3).sub.2                         162  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5     163  "      "      "           "    NH.sub.2                                  164  "      "      "           "    O.sup.- NH.sub.4.sup.+                    165  "      "      "           "    OCH.sub.2 Cl.sub.2 CH.sub.3               166  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3            167  "      "      "           "    O.sup.- K.sup.+                           168  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2              169  (iso)C.sub.4 H.sub.9                                                                 (iso)C.sub.4 H.sub.9                                                                 (iso)C.sub.4 H.sub.9                                                                      CH.sub.2                                                                           OH                                        170  "      "      "           "    OCH.sub.3                                 171  "      "      "           "    OC.sub.2 H.sub.5                          172  "      "      "           "    OC.sub.3 H.sub.7                          173  "      "      "           "    OCH(CH.sub.3).sub.2                       174  "      "      "           "    OC.sub.4 H.sub.9                          175  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5        176  "      "      "           "    OC.sub.6 H.sub.5                          177  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                 178  "      "      "           "    OCH.sub.2 CHCH.sub.2                      179  "      "      "           "    OCH.sub.2 CCH                             180  "      "      "           "    O.sup.- Na.sup.+                          181  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3              182  "      "      "           "    N(CH.sub.3).sub.2                         183  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5     184  "      "      "           "    NH.sub.2                                  185  "      "      "           "    O.sup.- NH.sub.4.sup.+                    186  "      "      "           "    OCH.sub.2 Cl.sub.2 CH.sub.3               187  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3            188  "      "      "           "    -O.sup.- K.sup.+                          189  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2              190  (n)C.sub.3 H.sub.7                                                                   (n)C.sub.3 H.sub.7                                                                   (n)C.sub.3 H.sub.7                                                                        CH.sub.2                                                                           OH                                        191  "      "      "           "    OCH.sub.3                                 192  "      "      "           "    OC.sub.2 H.sub.5                          193  "      "      "           "    OC.sub.3 H.sub.7                          194  "      "      "           "    OCH(CH.sub.3).sub.2                       195  "      "      "           "    OC.sub.4 H.sub.9                          196  "      "      "           "    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5        197  "      "      "           "    OC.sub.6 H.sub.5                          198  "      "      "           "    OCH.sub.2 C.sub.6 H.sub.5                 199  "      "      "           "    OCH.sub.2 CHCH.sub.2                      200  "      "      "           "    OCH.sub.2 CCH                             201  "      "      "           "    O.sup.- Na.sup.+                          202  "      "      "           "    OCH.sub.2 Si(CH.sub.3).sub.3              203  "      "      "           "    N(CH.sub.3).sub.2                         204  "      "      "           "    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5     205  "      "      "           "    NH.sub.2                                  206  "      "      "           "    O.sup.- NH.sub.4.sup.+                    207  "      "      "           "    OCH.sub.2 Cl.sub.2 CH.sub.3               208  "      "      "           "    OCH(CH.sub.3)CO.sub.2 CH.sub.3            209  "      "      "           "    O.sup.- K.sup.+                           210  "      "      "           "    OCH.sub.2 CH(CH.sub.3).sub.2              211  CH.sub.3                                                                             CH.sub.3                                                                             (iso)C.sub.3 H.sub.7                                                                      CH.sub.2                                                                           OCH.sub.3     1,4709                      212  "      "      "           "    OC.sub.2 H.sub.5                                                                            1,4693                      213  "      "      C(CH.sub.3).sub.2 CH(CH.sub.3).sub.2                                                      "    OCH.sub.3                                 214  "      "      "           "    OC.sub.2 H.sub.5                          215  CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                                                  "    OCH.sub.3                                 216  "      "      "           "    OC.sub.2 H.sub.5                          217  (n)C.sub.4 H.sub.9                                                                   (n)C.sub.4 H.sub.9                                                                   (n)C.sub.4 H.sub.9                                                                        "    OCH.sub. 3                                218  "      "      "           "    OC.sub.2 H.sub.5                          219  "      "      "           "    OH                                        220  CH.sub.3                                                                             CH.sub.3                                                                             (n)C.sub.8 H.sub.17                                                                       "    OH                                        221  "      "      "           "    OCH.sub.3                                 222  "      "      "           "    OC.sub.2 H.sub.5                          223  "      "      CH.sub.2 C.sub.6 H.sub.5                                                                  "    OH                                        224  "      "      "           "    OCH.sub.3                                 225  "      "      "           "    OC.sub.2 H.sub.5                          226  "      "      (n)C.sub.18 H.sub.37                                                                      "    OH                                        227  "      "      "           "    OCH.sub.3     wax                         228  "      "      "           "    OC.sub.2 H.sub.5                                                                            wax                         229  "      "      (n)C.sub.10 H.sub.21                                                                      "    OH                                        230  "      "      "           "    OCH.sub.3                                 231  "      "      "           "    OC.sub.2 H.sub.5                          232  CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2 CH.sub.2 C(CH.sub.3).sub.2 CH.sub.3                                              CH.sub.2                                                                           OH                                        233  "      "      "           "    OCH.sub.3                                 234  "      "      "           "    OC.sub.2 H.sub.5                          235  "      "      (iso)C.sub.3 H.sub.7                                                                      "    OH                                        236  "      "      C(CH.sub.3).sub.2 CH(CH.sub.3).sub.2                                                      "    OH                                        237  CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                                                  "    OH                                        238  CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                           "    OH                                        239  "      "      "           "    OCH.sub.3                                 240  "      "      "           "    OC.sub.2 H.sub.5                          241  CH.sub.3                                                                             CH.sub.3                                                                             (n)C.sub.3 H.sub.7                                                                        "    OH                                        242  "      "      "           "    OCH.sub.3                                 243  "      "      "           "    OC.sub.2 H.sub.5                          244  CH.sub.3                                                                             (n)C.sub.3 H.sub.7                                                                   (n)C.sub.3 H.sub.7                                                                        "    OH                                        245  "      "      "           "    OCH.sub.3                                 246  "      "      "           "    OC.sub.2 H.sub.5                          247  CH.sub.3                                                                             isoC.sub.3 H.sub.7                                                                   isoC.sub.3 H.sub.7                                                                        "    OH                                        248  "      "      "           "    OCH.sub.3                                 249  "      "      "           "    OC.sub.2 H.sub.5                          250  CH.sub.3                                                                             CH.sub.3                                                                             n-C.sub.4 H.sub.9                                                                         "    OH                                        251  "      "      "           "    OCH.sub.3                                 252  "      "      "           "    OC.sub.2 H.sub.5                          253  "      nC.sub.4 H.sub.9                                                                     nC.sub.4 H.sub.9                                                                          "    OH                                        254  "      "      "           "    OCH.sub.3                                 255  "      "      "           "    OC.sub.2 H.sub.5                          256  CH.sub.3                                                                             C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                           "    OH                                        257  "      "      "           "    OCH.sub.3                                 258  "      "      "           "    OC.sub.2 H.sub.5                          __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR7##                                       (2)                           Example                                                                            R.sup.1                                                                              R.sup.2                                                                              R.sup.3     Z               n.sub.D.sup.20                 __________________________________________________________________________    259  CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3    OH                                             260  "      "      "           OCH.sub.3       1,466                          261  "      "      "           OC.sub.2 H.sub.5                                                                              1,463                          262  "      "      "           OC.sub.3 H.sub.7                               263  "      "      "           OCH(CH.sub.3).sub.2                            264  "      "      "           OC.sub.4 H.sub.9                               265  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             266  "      "      "           OC.sub.6 H.sub.5                               267  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      268  "      "      "           OCH.sub.2 CHCH.sub.2                           269  "      "      "           OCH.sub.2 CCH                                  270  "      "      "           O.sup.- Na.sup.+                               271  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   272  "      "      "           N(CH.sub.3).sub.2                              273  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          274  "      "      "           NH.sub.2                                       275  "      "      "           O.sup.- NH.sub.4.sup.+                         276  "      "      "           OCH.sub.3 CO.sub.2 CH.sub.3                    277  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 278  "      "      "           O.sup.- K.sup.+                                279  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   280  CH.sub.3                                                                             CH.sub.3                                                                             C.sub.6 H.sub.5                                                                           OH                                             281  "      "      "           OCH.sub.3                                      282  "      "      "           OC.sub.2 H.sub.5                               283  "      "      "           OC.sub.3 H.sub.7                               284  "      "      "           OCH(CH.sub.3).sub.2                            285  "      "      "           OC.sub.4 H.sub.9                               286  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             287  "      "      "           OC.sub.6 H.sub.5                               288  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      289  "      "      "           OCH.sub.2 CHCH.sub.2                           290  "      "      "           OCH.sub.2 CCH                                  291  "      "      "           O.sup.- Na.sup.+                               292  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   293  "      "      "           N(CH.sub.3).sub.2                              294  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          295  "      "      "           NH.sub.2                                       296  "      "      "           O.sup.- NH.sub.4.sup.+                         297  "      "      "           OCH.sub.3 CO.sub.2 CH.sub.3                    298  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 299  "      "      "           O.sup.- K.sup.+                                300  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   301  CH.sub.3                                                                             CH.sub.3                                                                             C.sub.6 H.sub.5                                                                           OH                                             302  "      "      "           OCH.sub.3                                      303  "      "      "           OC.sub.2 H.sub.5                               304  "      "      "           OC.sub.3 H.sub.7                               305  "      "      "           OCH(CH.sub.3).sub.2                            306  "      "      "           OC.sub.4 H.sub.9                               307  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             308  "      "      "           OC.sub.6 H.sub.5                               309  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      310  "      "      "           OCH.sub.2 CHCH.sub.2                           311  "      "      "           OCH.sub.2 CCH                                  312  "      "      "           O.sup.- Na.sup.+                               313  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   314  "      "      "           N(CH.sub.3).sub.2                              315  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          316  "      "      "           NH.sub.2                                       317  "      "      "           O.sup.- NH.sub.4.sup.+                         318  "      "      "           OCH.sub.3 CO.sub.2 CH.sub.3                    319  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 320  "      "      "           O.sup.- K.sup.+                                321  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   322  C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      C.sub.6 H.sub.5                                                                           OH                                             323  "      "      "           OCH.sub.3                                      324  "      "      "           OC.sub.2 H.sub.5                               325  "      "      "           OC.sub.3 H.sub.7                               326  "      "      "           OCH(CH.sub.3).sub.2                            327  "      "      "           OC.sub.4 H.sub.9                               328  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             329  "      "      "           OC.sub.6 H.sub.5                               330  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      331  "      "      "           OCH.sub.2 CHCH.sub.2                           332  "      "      "           OCH.sub.2 CCH                                  333  "      "      "           O.sup.- Na.sup.+                               334  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   335  "      "      "           N(CH.sub.3).sub.2                              336  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          337  "      "      "           NH.sub.2                                       338  "      "      "           O.sup.- NH.sub.4.sup.+                         339  "      "      "           OCH.sub.3 CO.sub.2 CH.sub.3                    340  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 341  "      "      "           O.sup.- K.sup.+                                342  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   343  CH(CH.sub.3).sub.2                                                                   CH(CH.sub.3).sub.2                                                                   CH(CH.sub.3).sub.2                                                                        OH                                             344  "      "      "           OCH.sub.3                                      345  "      "      "           OC.sub.2 H.sub.5                               346  "      "      "           OC.sub.3 H.sub.7                               347  "      "      "           OCH(CH.sub.3).sub.2                            348  "      "      "           OC.sub.4 H.sub.9                               349  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             350  "      "      "           OC.sub.6 H.sub.5                               351  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      352  "      "      "           OCH.sub.2 CHCH.sub.2                           353  "      "      "           OCH.sub.2 CCH                                  354  "      "      "           O.sup.- Na.sup.+                               355  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   356  "      "      "           N(CH.sub.3).sub.2                              357  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          358  "      "      "           NH.sub.2                                       359  "      "      "           O.sup.- NH.sub.4.sup.+                         360  "      "      "           OCH.sub.2 Cl.sub.2 CH.sub.3                    361  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 362  "      "      "           O.sup.- K.sup.+                                363  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   364  C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                           OH                                             365  "      "      "           OCH.sub.3                                      366  "      "      "           OC.sub.2 H.sub.5                               367  "      "      "           OC.sub.3 H.sub.7                               368  "      "      "           OCH(CH.sub.3).sub.2                            369  "      "      "           OC.sub.4 H.sub.9                               370  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             371  "      "      "            OC.sub.6 H.sub.5                              372  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      373  "      "      "           OCH.sub.2 CHCH.sub.2                           374  "      "      "           OCH.sub.2 CCH                                  375  "      "      "           O.sup.- Na.sup.+                               376  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   377  "      "      "           N(CH.sub.3).sub.2                              378  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          379  "      "      "           NH.sub.2                                       380  "      "      "           O.sup.- NH.sub.4.sup.+                         381  "      "      "           OCH.sub.3 CO.sub.2 CH.sub.3                    382  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 383  "      "      "           O.sup.- K.sup.+                                384  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   385  CH.sub.3                                                                             CH.sub.3                                                                             (t)-C.sub.4 H.sub.9                                                                       OH                                             386  "      "      "           OCH.sub.3                                      387  "      "      "           OC.sub.2 H.sub.5                               388  "      "      "           OC.sub.3 H.sub.7                               389  "      "      "           OCH(CH.sub.3).sub.2                            390  "      "      "           OC.sub.4 H.sub.9                               391  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             392  "      "      "           OC.sub.6 H.sub.5                               393  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      394  "      "      "           OCH.sub.2 CHCH.sub.2                           395  "      "      "           OCH.sub.2 CCH                                  396  "      "      "           O.sup.- Na.sup.+                               397  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   398  "      "      "           N(CH.sub.3).sub.2                              399  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          400  "      "      "           NH.sub.2                                       401  "      "      "           O.sup.- NH.sub.4.sup.+                         402  "      "      "           OCH.sub.3 CO.sub.2 CH.sub.3                    403  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 404  "      "      "           O.sup.- K.sup.+                                405  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   406  (n)C.sub.6 H.sub.13                                                                  (n)C.sub.6 H.sub.13                                                                  (n)C.sub.6 H.sub.13                                                                       OH                                             407  "      "      "           OCH.sub.3                                      408  "      "      "           OC.sub.2 H.sub.5                               409  "      "      "           OC.sub.3 H.sub.7                               410  "      "      "           OCH(CH.sub.3).sub.2                            411  "      "      "           OC.sub.4 H.sub.9                               412  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             413  "      "      "           OC.sub.6 H.sub.5                               414  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      415  "      "      "           O CH.sub.2 CHCH.sub.2                          416  "      "      "           OCH.sub.2 CCH                                  417  "      "      "           O.sup.- Na.sup.+                               418  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   419  "      "      "           N(CH.sub.3).sub.2                              420  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          421  "      "      "           NH.sub.2                                       422  "      "      "           O.sup.- NH.sub.4.sup.+                         423  "      "      "           OCH.sub.2 Cl.sub.2 CH.sub.3                    424  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 425  "      "      "           O.sup.- K.sup.+                                426  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   427  (iso)C.sub.4 H.sub.9                                                                 (iso)C.sub.4 H.sub.9                                                                 (iso)C.sub.4 H.sub.9                                                                      OH                                             428  "      "      "           OCH.sub.3                                      429  "      "      "           OC.sub.2 H.sub.5                               430  "      "      "           OC.sub.3 H.sub.7                               431  "      "      "           OCH(CH.sub.3).sub.2                            432  "      "      "           OC.sub.4 H.sub.9                               433  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             434  "      "      "           OC.sub.6 H.sub.5                               435  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      436  "      "      "           OCH.sub.2 CHCH.sub.2                           437  "      "      "           OCH.sub.2 CCH                                  438  "      "      "           O.sup.- Na.sup.+                               439  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   440  "      "      "           N(CH.sub.3).sub.2                              441  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          442  "      "      "           NH.sub.2                                       443  "      "      "           O.sup.- NH.sub.4.sup.+                         444  "      "      "           OCH.sub.2 Cl.sub.2 CH.sub.3                    445  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 446  "      "      "           O.sup.- K.sup.+                                447  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   448  (n)C.sub.3 H.sub.7                                                                   (n)C.sub.3 H.sub.7                                                                   (n)C.sub.3 H.sub.7                                                                        OH                                             449  "      "      "           OCH.sub.3                                      450  "      "      "           OC.sub.2 H.sub.5                               451  "      "      "           OC.sub.3 H.sub.7                               452  "      "      "           OCH(CH.sub.3).sub.2                            453  "      "      "           OC.sub.4 H.sub.9                               454  "      "      "           OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5             455  "      "      "           OC.sub.6 H.sub.5                               456  "      "      "           OCH.sub.2 C.sub.6 H.sub.5                      457  "      "      "           OCH.sub.2 CHCH.sub.2                           458  "      "      "           OCH.sub.2 C CH                                 459  "      "      "           O.sup.- Na.sup.+                               460  "      "      "           OCH.sub.2 Si(CH.sub.3).sub.3                   461  "      "      "           N(CH.sub.3).sub.2                              462  "      "      "           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5          463  "      "      "           NH.sub.2                                       464  "      "      "           O.sup.- NH.sub.4.sup.+                         465  "      "      "           OCH.sub.2 Cl.sub.2 CH.sub.3                    466  "      "      "           OCH(CH.sub.3)CO.sub.2 CH.sub.3                 467  "      "      "           O.sup.- K.sup.+                                468  "      "      "           OCH.sub.2 CH(CH.sub.3).sub.2                   469  CH.sub.3                                                                             CH.sub.3                                                                             (iso)C.sub.3 H.sub.7                                                                      OCH.sub.3                                      470  "      "      "           OC.sub.2 H.sub.5                               471  "      "      C(CH.sub.3).sub.2 CH(CH.sub.3).sub.2                                                      OCH.sub.3                                      472  "      "      "           OC.sub.2 H.sub.5                               473  CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub. 2 C.sub.6 H.sub.5                                                            CH.sub.2 C.sub.6 H.sub.5                                                                  OCH.sub.3                                      474  "      "      "           OC.sub.2 H.sub.5                               475  (n)C.sub.4 H.sub.9                                                                   (n)C.sub.4 H.sub.9                                                                   (n)C.sub.4 H.sub.9                                                                        OCH.sub.3                                      476  "      "      "           OC.sub.2 H.sub.5                               477  "      "      "           OH                                             478  CH.sub.3                                                                             CH.sub.3                                                                             (n)C.sub.8 H.sub.17                                                                       OH                                             479  "      "      "           OCH.sub.3                                      480  "      "      "           OC.sub.2 H.sub.5                               481  "      "      CH.sub.2 C.sub.6 H.sub.5                                                                  OH                                             482  "      "      "           OCH.sub.3                                      483  "      "      "           OC.sub.2 H.sub.5                               484  "      "      (n)C.sub.18 H.sub.37                                                                      OH                                             485  "      "      "           OCH.sub.3                                      486  "      "      "           OC.sub.2 H.sub.5                               487  "      "      (n)C.sub.10 H.sub.21                                                                      OH                                             488  "      "      "           OCH.sub.3                                      489  "      "      "           OC.sub.2 H.sub.5                               490  CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.2 CH.sub.2 C(CH.sub.3).sub.2 CH.sub.3                                              OH                                             491  "      "      "           OCH.sub.3                                      492  "      "      "           OC.sub.2 H.sub.5                               493  "      "      (iso)C.sub.3 H.sub.7                                                                      OH                                             494  "      "      C(CH.sub.3).sub.2 CH(CH.sub.3).sub.2                                                      OH                                             495  CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                                                  OH                                             496  CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                           OH                                             497  "      "      "           OCH.sub.3                                      498  "      "      "           OC.sub.2 H.sub.5                               499  CH.sub.3                                                                             CH.sub.3                                                                             (n)C.sub.3 H.sub.7                                                                        OH                                             500  "      "      "           OCH.sub.3                                      501  "      "      "           OC.sub.2 H.sub.5                               502  CH.sub.3                                                                             (n)C.sub.3 H.sub.7                                                                   (n)C.sub.3 H.sub.7                                                                        OH                                             503  "      "      "           OCH.sub.3                                      504  "      "      "           OC.sub.2 H.sub.5                               505  CH.sub.3                                                                             isoC.sub.3 H.sub.7                                                                   isoC.sub.3 H.sub.7                                                                        OH                                             506  "      "      "           OCH.sub.3                                      507  "      "      "           OC.sub.2 H.sub.5                               508  CH.sub.3                                                                             CH.sub.3                                                                             n-C.sub. 4 H.sub.9                                                                        OH                                             509  "      "      "           OCH.sub.3                                      510  "      "      "           OC.sub.2 H.sub.5                               511  "      nC.sub.4 H.sub.9                                                                     n-C.sub. 4 H.sub.9                                                                        OH                                             512  "      "      "           OCH.sub.3                                      513  "      "      "           OC.sub.2 H.sub.5                               514  CH.sub.3                                                                             C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                           OH                                             515  "      "      "           OCH.sub.3                                      516  "      "      "           OC.sub.2 H.sub.5                               __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                         ##STR8##                      (3)                                            Ex-                                                                           am-                                                                           ple  R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                            X   A      B        Z                                 ______________________________________                                        421  CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                           O   --     CH.sub.2 OCH.sub.3                         422  "      "      "    "   "      "        OC.sub.2 H.sub.5                  423  "      "      "    "   CH.sub.2                                                                             "        OCH.sub.3                         424  "      "      "    "   "      "        OC.sub.2 H.sub.5                  425  "      "      "    "   --     CH.sub.2 CH.sub.2                                                                      OC.sub.2 H.sub.5                  426  "      "      "    "   CH.sub.2                                                                             "        OC.sub.2 H.sub.5                  427  "      "      "    "   "      "         OCH.sub.3                        428  "      "      "    S   CH.sub.2                                                                             --       OCH.sub.3                         429  "      "      "    "   "      "        OC.sub.2 H.sub.5                  430  "      "      "    "   --     --       OCH.sub.3                         431  "      "      "    "   "      "        OC.sub.2 H.sub.5                  432  "      "      "    "   --     CH.sub.2 OCH.sub.3                         433  "      "      "    "   --     CH.sub.2 OC.sub.2 H.sub.5                  434  "      "      "    O   CH.sub.2 CH.sub.2                                                                    --       OCH.sub.3                         435  "      "      "    "   "      --       OC.sub.2 H.sub.5                  436  "      "      "    "   "      CH.sub.2 OCH.sub.3                         437  "      "      "    "   "      CH.sub.2 OC.sub.2 H.sub.5                  ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR9##                      (4)                                            Example                                                                              R.sup.1 R.sup.2                                                                              R.sup.3                                                                             A    B     X    Z                                 ______________________________________                                        438    CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3                                                                            --   --    O    OCH.sub.3                         439    "       "      "     "    "     "    OC.sub.2 H.sub.5                  440    "       "      "     CH.sub.2                                                                           --    O    OCH.sub.3                         441    "       "      "     "    "     "    OC.sub.2 H.sub.5                  442    "       "      "     "    CH.sub.2                                                                            "    OCH.sub.3                         443    "       "      "     "    "     "    OC.sub.2 H.sub.5                  444    "       "      "     --   CH.sub.2                                                                            "    OCH.sub.3                         445    "       "      "     --   CH.sub.2                                                                            "     OC.sub.2 H.sub.5                 446    "       "      "     --   --    S    OCH.sub.3                         447    "       "      "     "    "     "    OC.sub.2 H.sub.5                  448    "       "      "     CH.sub.2                                                                           --    "    OCH.sub.3                         449    "       "      "     "    "     "    OC.sub.2 H.sub.5                  450    "       "      "     CH.sub.2                                                                           CH.sub.2                                                                            "    OCH.sub.3                         451    "       "      "     "    "     "    OC.sub.2 H.sub.5                  452    "       "      "     --   CH.sub.2                                                                            "    OCH.sub.3                         453    "       "      "     "    "     "    OC.sub.2 H.sub.5                  ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________     ##STR10##                           (5)                                      Example                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          A   B  X  Z        mp/n.sub.D.sup.20                           __________________________________________________________________________    454   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         --  -- O  OCH.sub.3                                            455   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     456   "  "  "  CH.sub.2                                                                          -- O  OCH.sub.3                                            457   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     458   "  "  "  "   CH.sub.2                                                                         "  OCH.sub.3                                            459   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     460   "  "  "  --  CH.sub.2                                                                         "  OCH.sub.3                                            461   "  "  "  --  CH.sub.2                                                                         "  OC.sub.2 H.sub.5                                     462   "  "  "  --  -- S  OCH.sub.3                                            463   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     464   "  "  "  CH.sub.2                                                                          -- "  OCH.sub.3                                            465   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     466   "  "  "  CH.sub.2                                                                          CH.sub.2                                                                         "  OCH.sub.3                                            467   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     468   "  "  "  --  CH.sub.2                                                                         "  OCH.sub.3                                            469   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     479   "  "  "  CH.sub.2                                                                          CH.sub.2                                                                         O  CH.sub.2 CCH                                         471   "  "  "  --  -- "  CH.sub.2 CCH                                         472   "  "  "  CH.sub.2                                                                          -- "  CH.sub.2 CCH                                         473   "  "  "  --  CH.sub.2                                                                         "  CH.sub.2 CCH                                         474   "  "  "  --  -- S  CH.sub.2 CCH                                         475   "  "  "  --  -- S  CH.sub.2 CHCH.sub.2                                  476   "  "  "  --  -- O  CH.sub.2 CHCH.sub.2                                  477   "  "  "  --  -- O  (CH.sub.2).sub.3 CH.sub.3                            478   "  "  "  --  -- S  (CH.sub.2).sub.3 CH.sub.3                            479   "  "  "  --  -- S  OH                                                   480   "  "  "  --  -- O  OH                                                   481   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.2                                                                          CH.sub.2                                                                         O  OH                                                   482   "  "  "  CH.sub. 2                                                                         -- O  OH                                                   483   "  "  "  --  CH.sub.2                                                                         O  OH                                                   484   "  "  "  --  CH.sub.2                                                                         S  OH                                                   485   "  "  "  CH.sub.2                                                                          -- S  OH                                                   __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________     ##STR11##                           (6)                                      Example                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          A   B  X  Z        mp/n.sub.D.sup.20                           __________________________________________________________________________    486   "  "  "  --  -- O  OH                                                   487   "  "  "  --  -- S  OH                                                   488   "  "  "  CH.sub.2                                                                          CH.sub.2                                                                         O  OH                                                   489   "  "  "  CH.sub.2                                                                          -- O  OH                                                   490   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         --  -- O  OCH.sub.3                                            491   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     492   "  "  "  CH.sub.2                                                                          -- O  OCH.sub.3                                            493   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     494   "  "  "  "   CH.sub.2                                                                         "  OCH.sub.3                                            495   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     496   "  "  "  --  CH.sub.2                                                                         "  OCH.sub.3                                            497   "  "  "  --  CH.sub.2                                                                         "  OC.sub.2 H.sub.5                                     498   "  "  "  --  -- S  OCH.sub.3                                            499   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     500   "  "  "  CH.sub.2                                                                          -- "  OCH.sub.3                                            501   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     502   "  "  "  CH.sub.2                                                                          CH.sub.2                                                                         "  OCH.sub.3                                            503   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     504   "  "  "  --  CH.sub.2                                                                         "  OCH.sub.3                                            505   "  "  "  "   "  "  OC.sub.2 H.sub.5                                     506   "  "  "  CH.sub.2                                                                          CH.sub.2                                                                         O  CH.sub.2 CCH                                         507   "  "  "  --  -- "  CH.sub.2 CCH                                         508   "  "  "  CH.sub.2                                                                          -- "  CH.sub.2 CCH                                         509   "  "  "  --  CH.sub.2                                                                         "  CH.sub.2 CCH                                         510   "  "  "  --  -- S  CH.sub.2 CCH                                         511   "  "  "  --  -- S  CH.sub.2 CHCH.sub.2                                  512   "  "  "  --  -- O  CH.sub.2 CHCH.sub.2                                  513   "  "  "  --  -- O  (CH.sub.2).sub.3 CH.sub.3                            514   "  "  "  --  -- S  (CH.sub.2).sub.3 CH.sub. 3                           __________________________________________________________________________

C. Biological Examples

Wheat and barley were grown in plastic pots in a greenhouse until theyhad reached the 3-4 leaf stage, and then treated with the compoundsaccording to the invention and herbicides, using the post-emergencemethod. For this purpose, the herbicides and the compounds of theformula (I) were applied in the form of aqueous suspensions oremulsions, at an application rate of water of 800 l/ha (converted). 3-4weeks after the treatment, the plants were visually scored for any typeof damage caused by the herbicides applied, the extent of sustainedgrowth inhibition being particularly taken into account. For theassessment, percentages in comparison with untreated controls were used.

The results from Table 7 show that the compounds according to theinvention are capable of effectively reducing severe herbicide damage oncrop plants.

Even when far too high doses of the herbicides are applied, severedamage which occurs in the crop plants is markedly reduced, and lesserdamage is eliminated completely. Mixtures of herbicides and compoundsaccording to the invention are therefore highly suitable for selectivelycontrolling weeds in cereal crops.

                  TABLE 7                                                         ______________________________________                                        Safener action of the compounds according to the invention                    Herbicide (H)                                                                              Dosage rate  Damage to                                             +            in         crop plant (%)                                      safener No.  kg of a.i./ha                                                                              TRAE    HOVU                                        ______________________________________                                        H            2.0          80      --                                                       0.2          --      85-90                                       H + 2        2.0 + 1.25   20      --                                          H + 3        0.2 + 1.25   --      30                                          H + 4        2.0 + 1.25   25      --                                          H + 261      0.2 + 1.25   --      35                                          ______________________________________                                         Abbreviations:                                                                TRAE = Triticum aestivum (wheat)                                              HOVU = Hordeum vulgare (barley)                                               a.i. = active ingredient (i.e. based on pure active substance)                H = ethyl 2(4-(6-chlorobenzoxazol-2-yloxy)phenoxypropionate                   (fenoxapropethyl)                                                             Safener No. = No. of the Preparation Example of Tables 1-6               

We claim:
 1. A compound of the formula (I) and salts thereof

    (R.sup.1)(R.sup.2)(R.sup.3)Si--A--Het--B--CO--Z            (I)

in which Het is a divalent heterocyclic radical from the groupcomprising the isothiazolines, isothiazoles or isoxazoles, andisoxazolines of the formulae (Ia) to (Id), ##STR12## in which X is anoxygen or sulfur atom, A and B independently of one another in each caseare a single bond or C₁ -C₄ -alkylene which is unsubstituted ormonosubstituted or polysubstituted by C₁ -C₄ -alkyl, R¹, R² and R³independently of one another are alkyl, alkenyl, alkynyl or cycloalkyl,it being possible for the four last-mentioned radicals to beunsubstituted or mono- or polysubstituted by radicals from the groupcomprising alkoxy, alkylthio, mono- or dialkylamino, alkoxycarbonyl,alkylcarbonyloxy, cyano and halogen, furthermore phenylalkyl or phenylwhich in each case are unsubstituted or mono- or polysubstituted in thephenyl radical by radicals from the group comprising alkyl, alkoxy,alkylthio, mono- and dialkylamino, alkoxycarbonyl, cyano and halogen, Zis hydroxyl or alkoxy, alkenyloxy, alkynyloxy, alkylthio, cycloalkoxy,phenoxy or benzyloxy, the 7 last-mentioned radicals being unsubstitutedor mono- or polysubstituted by radicals from the group comprisingalkoxy, alkylthio, mono- and dialkylamino, phenyl, substituted phenyl,cyano, halogenoalkyl, halogenoalkoxy and halogen, furthermoretrialkylsilylmethoxy, a radical of the formula (Ie) or (If) ##STR13##where R is hydrogen or alkyl, Z¹ radicals independently of one anotherare halogen, haloalkyl, haloalkoxy, alkyl, alkoxy or alkylthio and n isan integer from 0 to 5, or Z is furthermore amino, mono- ordialkylamino, cycloalkylamino, hydrazino, alkyl- or dialkylhydrazino,pyridino, morpholino, dimethylmorpholino, a radical of the formula (Ig),##STR14## where R⁴ and R⁵ independently of one another are alkylradicals or R⁴ and R⁵ together with the carbon atom linking them forte acycloalkyl radical, furthermore a radical of the formula (Ih), ##STR15##where R⁶ and R⁷ independently of one another are hydrogen or a saturatedor unsaturated acyclic hydrocarbon radical.
 2. A compound and saltsthereof as claimed in claim 1, in whichZ is hydroxyl, C₁ -C₆ -alkoxy, C₂-C₆ -alkenyloxy, C₂ -C₆ -alkynyloxy, C₁ -C₆ -alkylthio, C₃ -C₆-cycloalkoxy, phenoxy or benzyloxy, the 7 last-mentioned radicals beingunsubstituted or mono- or polysubstituted by radicals from the groupcomprising C₁ -C₄ -alkoxy, mono- or di-(C₁ -C₄ -alkyl)amino, C₁ -C₄-alkylthio, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy, cyano and halogen, orZ is furthermore tri(C₁ -C₄ -alkyl)silylmethoxy, furthermore a radicalof the formula (Ie) or (If) mentioned, in which R in each case ishydrogen or (C₁ -C₄)-alkyl, Z¹ is halogen and n is 0, 1, 2, 3, 4 or 5,or Z is furthermore amino, mono- or di-(C₁ -C₄ -alkyl)-amino, C₅ -C₆-cycloalkylamino, hydrazino, piperidino, morpholino or2,6-dimethylmorpholino, a radical of the formula (Ig) mentioned where R⁴and R⁵ independently of one another are C₁ -C₄ -alkyl or R¹ and R²together with the carbon atom linking them form a 5-, 6- or 7-memberedcycloalkyl radical, or Z is a radical of the formula (Ih) mentionedwhere R⁶ and R⁷ independently of one another are hydrogen or C₁ -C₆-alkyl, C₂ -C₆ -alkyl or C₂ -C₆ -alkynyl.
 3. A compound and saltsthereof as claimed in claim 2, in whichR¹, R² and R³ independently ofone another are C₁ -C₁₈ -alkyl, C₂ -C₁₈ -alkenyl, C₂ -C₈ -alkynyl or C₃-C₈ -cycloalkyl, the 4 last-mentioned radicals being unsubstituted ormono- or polysubstituted by radicals from the group comprising C₁ -C₄-alkyl, C₁ -C₄ -alkylthio, mono- or di-(C₁ -C₄ -alkyl)amino, (C₁ -C₄-alkoxy)carbonyl, (C₁ -C₄ -alkyl)carbonyloxy, cyano and halogen,furthermore phenyl-(C₁ -C₄ -alkyl) or phenyl, the 2 last-mentionedradicals being unsubstituted or mono- or polysubstituted by radicalsfrom the group comprising C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, mono- and di-(C₁ -C₄ -alkyl)amino, cyano and halogen.
 4. Acompound and salts thereof as claimed in claim 3, in whichZ is hydroxyl,C₁ -C₄ -alkoxy, C₂ -C₄ -alkynyloxy, C₂ -C₄ -alkynyloxy, C₁ -C₄-alkylthio, phenoxy or benzyloxy, the 6 last-mentioned radicals beingunsubstituted or mono- or polysubstituted by radicals from the groupcomprising C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, mono- ordi-(C₁ -C₄ -alkyl)amino, cyano and halogen, furthermore tri-(C₁ -C₂-alkyl)silylmethoxy, a radical of the formula (Ie) or (If) mentionedwhere R is hydrogen or C₁ -C₄ -alkyl, Z¹ is halogen and n is 0-5,furthermore mono- and di-(C₁ -C₄ -alkyl)amino, C₅ -C₆ -cycloalkylamino,a radical of the formula (Ih) mentioned where R⁶ is C₁ -C₄ -alkyl, C₂-C₄ -alkenyl or C₂ -C₆ -alkynyl and R⁷ is hydrogen or methyl.
 5. Acompound and salts thereof as claimed in one of claims 1 to 4, in whichAis a direct bond or C₁ -C₂ -alkylene, preferably a direct bond or CH₂,and B is a direct bond or C₁ -C₂ -alkylene.
 6. A plant-protecting orplant-growth-regulating agent which contains a compound of the formula(I) or salts thereof, as claimed in claim 1, and inert additives orformulation auxiliaries.
 7. A selective herbicidal agent, which containsone or more herbicides in combination with a compound of the formula (I)or salts thereof, as defined in claim
 1. 8. An agent as claimed in claim7, which contains, as herbicides, one or more active substances from thegroup comprising carbamates, thiocarbonates, haloacetanilides,substituted phenoxy-, naphthoxy-, phenoxyphenoxy-, benzyloxyphenoxy- andheteroaryloxyphenoxy-carboxylic acid derivatives and cyclohexanedionederivatives.
 9. A method of selectively controlling undesired plants incrops of useful plants, which comprises applying, to the plants, seedsof plants or the area under cultivation, a herbicide in combination withcompounds of the formula (I) or salts thereof, as defined in claim 1.10. A method of protecting useful plants against phytotoxic side effectsof herbicides, which comprises applying, to the plants, seeds of plantsor the area under cultivation, herbicides in combination with compoundsof the formula (I) or salts thereof, as defined in claim
 1. 11. Acompound and salts thereof as claimed in claim 5, wherein A is a directbond or CH₂, and B is a direct bond or CH₂.
 12. A plant-protecting orplant-growth-regulating agent which contains a compound of the formula(I) or salts thereof, as claimed in claim 11, and inert additives orformulation auxiliaries.
 13. A selective herbicidal agent, whichcontains one or more herbicides selected from the group consisting ofcarbamates, thiocarbamates, haloacetanilides, substituted phenoxy-,naphthoxy-, phenoxyphenoxy-, benzyloxyphenoxy- andheteroaryloxyphenoxy-carboxylic acid derivatives and cyclohexanedionederivatives, in combination with the compound of formula (I) as definedin claim
 11. 14. A selective herbicidal agent as claimed in claim 13,wherein the herbicide is selected from the group consisting ofheteroaryloxyphenoxy-carboxylic acid derivatives.